The best-fit size and geometry of metal ions for coordination with nitrogen-donor macrocycles

The technique of calculating the strain energy of metal ion complexes as a function of metal to ligand bond length (Hancock and McDougall, J. Am. Chem. Soc., 102 (1980) 6553) is used to study best-fit sizes of metal ions for coordinating with tetraaza and triaza macrocyles. In addition to varying the metal to ligand bond length in the calculations, different coordination geometries of the metal ion are also examined. The metal to nitrogen (M-N) bond lengths, and coordination geometries, that give lowest energies for several N-donor macrocyles, are calculated by molecular mechanics, and 16-aneN₄ (1,5,9,13-tetraazacyclohexadecane) is found, contrary to popular belief, to coordinate best with very small metal ions, with lowest energy occurring for a slightly flattened tetrahedral metal ion of M-N length = 1.81 Å. The best-fit size and geometry for coordination in 12-aneN₄ (1,4,7,10-tetraazacyclotetradecane) is an M-N length of 2.15 Å and square pyramidal geometry, and with cyclam (1,4,8,11-tetraazacyclotetradecane) an M-N length of 2.06 Å and planar coordination that is approximately square.